Homogeneous liquid saccharide and oil systems

ABSTRACT

Oil based emulsifiable concentrates containing a liquid saccharide including a) at least one oil component; b) at least one saccharide, particularly a liquid saccharide solution (LS); c) and at least one non-ionic surfactant. The concentrate may also contain at least one of d) at least one surfactant hydrocarbyl saccharide; or e) at least one anionic surfactant; or f) at least one additional oil soluble non-ionic surfactant. The concentrates are typically homogeneous for at least 24 hours and emulsify readily on dilution into water. The concentrates may also contain an antifoaming agent especially a polysiloxane. Upon dilution in water, the emulsions formed from the concentrates are applied to substrates in combination with agrochemically active ingredients, preferably N-phosphonomethylglycine in the form of its soluble salts, to control weeds.

BACKGROUND OF THE INVENTION

Agrochemical compositions have been used to improve the quality andquantity of farm grown products. In this regard they can enhancebiological activity and act as nutrients, growth regulators and/orpesticides, for instance as herbicides, insecticides, fungicides, oracaricides. However, since they are expensive to make and purchase, itis desirable to reduce their overall cost in use by improving theireffectiveness in a unit area treated with the agrochemical.

In order to improve or enhance the effectiveness of many agrochemicals,certain materials are added to water-based agricultural spray mixturescontaining the agrochemical and concurrently applied to agriculturalsubstrates. These materials are commonly identified as agriculturalspray adjuvants and exist in a wide variety of forms and compositionsthat are used today in commercial agriculture. These adjuvant productsare used to provide a broad array of effects in typical use including,but not limited to, foam control, enhancement of the effectiveness of aspecific agrochemical, and/or modification of the agricultural spraymixture for either improved stability or modulation of spray dropletdiameter.

In the United States, most economically advantageous adjuvant productsused to improve or enhance the efficacy of an agrochemical, primarily apesticide, are supplied as liquids. The preferred liquid adjuvantproducts (for both convenience and economy) manufactured and sold in theUS are supplied as concentrated liquids and fall into two primarycategories. These categories are: (1) self-emulsifying oil andsurfactant compositions more commonly identified as Crop OilConcentrates (COC), and (2) readily water soluble or dispersiblesurfactant formulations known as concentrated liquid Non-IonicSurfactants (NIS). Commercial distribution channels in the USefficiently transport large volumes of such products, primarily in bulkform, making COC and NIS type products very economical for theirintended use. By improving the efficacy of the more costly pesticidethrough its combination in spray mixtures with an economicallyadvantageous, primarily low cost, adjuvant product, the overalleconomics of commercial agriculture can be improved. Use of effectiveadjuvant products in this manner decreases the seasonal cost to produceagricultural commodities and may also improve commodity yields, offeringeconomic benefits to those who use them.

One of the largest single groups of such effective liquid adjuvantproducts sold in the United States (by volume) is a COC compositioncontaining between 60 and 90% of a suitable agricultural grade ofmineral oil; an alternate form of this adjuvant type contains avegetable oil or methylated seed oil. All commercially significant formsof this adjuvant type commonly contain an oil soluble emulsifiercomposition composed of a blend of anionic and/or non-ionic surfactantsthat provides self-emulsification of the oil component upon dilution ina water-based agricultural spray mixture; the total surfactantconcentration in a typical COC product can range from 1 to 40%, mosttypically between 10 and 17%.

While the oil and surfactant composition in a COC adjuvant product couldalso be offered as a pre-emulsified system in water (an oil-in-wateremulsion), the added cost of production for an emulsified adjuvantproduct tends to make it less economically advantageous than theequivalent volume of oil adjuvant offered as a COC. Water based systemsalso have the undesirable characteristics of being generally morecomplicated to develop and manufacture and of requiring the use ofdiscrete thickening, preserving, and anti-freeze systems due to thetendency of water based emulsions to support microbial growth, cream orsettle/sediment, and deteriorate over time or during the freeze-thawcycle. The effect of including water as the dispersing medium alsodilutes the active components (oil and surfactant composition) makingthe system more expensive to deliver in the field on a pound of “active”adjuvant basis. Logistics costs also increase on this basis as morewater is shipped than may otherwise be present in a comparable COC typesystem.

In recent times, there have been specific improvements upon thecost-effectiveness of the described economically advantageous crop oilconcentrates. Most of these improvements have focused on two aspects ofthe composition. The first aspect is increasing the total concentrationof oil soluble surfactant emulsifier which has resulted in a change inpreferred surfactant concentration from 12-17% ten years ago toapproximately 40% at the current time; this change was associated with areduction in the amount of COC adjuvant product applied per unit areaand resulted in improved cost-in-use attributes for the adjuvant. Thesecond aspect is the selection of specific surfactant types based onboth field data and scientific judgement; this change was associatedwith improved performance of the adjuvant product with specificpesticide products. PCT Publication WO 95 03881 by Auda et al describesan agrochemical crop oil concentrate containing an oil or oils,hydrocarbyl saccharide surfactant, and additional non-ionic surfactantthat emulsifies readily upon dilution in water. This COC adjuvantcomposition was associated with enhancement or improvement of weedcontrol performance in conjunction with with soluble salts ofN-phosphonomethylglycine.

More recently, U.S. Pat. No. 5,945,377 to Penner describes compositionsincorporating a postemergence herbicide and a monosaccharide,particularly fructose, as a potentiator of the herbicide against weedswithout decreasing tolerance of a crop plant to the herbicide. Thecompositions are used as a spray in water in a method for killing weeds.Although not considered an NIS adjuvant, corn syrup was evaluated as anadjuvant with several postemergence herbicides in the greenhouse andfield studies. The greatest enhancement of herbicide activity wasobserved with high fructose corn syrup applied in combination with anammonium sulfate and an effective non-ionic adjuvant with anionicherbicides such as glyphosate and glufosinate for control of grassspecies such as giant foxtail. The efficacy of the corn syrup as anadjuvant was both weed and herbicide specific.

The previously mentioned publication (WO 95 03881) describesself-dispersing alkylpolysaccharide surfactants in crop oil concentrates(COC's). These compositions did not include additional aqueous liquidnon-surfactant polysaccharide components which have been found recentlyto promote the herbicidal activity of glyphosate. It was concluded thata robust, single phase composition containing: (1) an oil adjuvant, (2)a saccharide adjuvant, and (3) an optimal amount of surfactant with acorresponding minimum of additional water could allow the delivery of ahighly concentrated liquid agricultural adjuvant product with a totalsurfactant concentration similar to those in use today (ca. 10-40% w/w).The successful incorporation of the inexpensive and efficacioussaccharide adjuvant would improve the cost-effectiveness of the finishedadjuvant product. The resulting product is commercially advantageous forthe manufacturer and economically beneficial to the purchaser/user. Anadditional advantage for combining the saccharide and surfactantadjuvant composition with the traditional COC adjuvant composition wouldbe the significant commercial advantage obtained by being able toprovide one very broadly effective adjuvant composition having thepreferred characteristics of the COC, NIS, and newer saccharide adjuvanttypes.

The compositions described are intended as commercial alternatives totraditional 17 and 40% surfactant in oil based COC adjuvants used in theagricultural market. These COC adjuvant types, although cost-effectivefor use with most water-dipsersible agrochemicals, are not the mosteffective type of adjuvant for the soluble salts ofN-phosphonomethylglycine, most commonly called glyphosate, whichrepresents the largest commercial pesticide sold in the US and as aresult presents the largest single adjuvant sales opportunity. The mostefficacious NIS adjuvants for use with glyphosate, identified asethoxylated tallow alkylamines, are for the current time typicallycombined into concentrated glyposate solution products and are thereforenot readily accessible to adjuvant products intended for combinationinto agricultural spray mixtures. With the expiration of patents onconcentrated glyphosate salt solution products, other forms of thepesticide, including products which intentionally do not include thepreferred NIS adjuvant as a means to reduce the cost of formulatedglyphosate and increase its concentration in solution products may alsobecome available. It would be advantageous to alter the traditional COCproduct or the COC product described in WO 95 03881 to demonstrateimproved efficacy enhancement with glyphosate products; this would behighly desireable as a means of expanding the market for the highlycost-effective COC adjuvant product.

Ideally it is desireable to achieve a surfactant composition that servesas both the combined COC adjuvant self-emulsifier andcompatibilizer/stabilizer for the saccharide component and which alsohas the ability to stabilize and self-emulsify the oil alone (withoutthe saccharide component) as well as having special advantages in thatit offers improved economies in the purchase of a single surfactantcomposition and in enabling the flexible manufacturing of COC adjuvantsin the same surfactant composition both with and without added liquidsaccharide components. Since the corn syrup adjuvant also requiresconcurrent application of a nonionic surfactant adjuvant for optimumperformance, the direct combination of the oil and corn syrup with asingle surfactant system that would both “activate” the saccharide andconcurrently emulsify the oil component would have the greatest economicand competitive advantage. Essentially, by using the combined COC andsaccharide NIS product concept, the composition would be 100% activewith a minimum total concentration of the surfactant compositionrequired for optimum performance. Since the surfactant constitutes themost costly input for manufacturing on a component purchased price (perpound) basis, reducing surfactant to the minimum required for optimalactivity is highly desireable.

The greatest difficulty in developing the combined saccharide COCadjuvant product is the identification of suitable surfactant systemswhich would enable the formulation of homogeneous compositions thatwould function both as robust stabilizers for a highly concentratedliquid saccharide solution in an oil adjuvant and which would providethe self-emulsification upon dilution that is required. These twoopposing effects must be delivered in one adjuvant product with aminimum of total surfactant. Preferably a foam control agent would alsobe included in the composition.

In U.S. Pat. No. 5,885,646 to Wong, there is described a process forpreparing nut spreads having a sugar level of from about 15 to about 50%and especially flavored nut spreads having such relatively high levelsof sugar. A substantially homogeneous blend is prepared from a fluidsuspension consisting essentially of an intimate mixture of sugar,liquid oil and lecithin as a surfactant to improve the fluidity of thesuspension, a nut solids-containing mixture and a flavorant that ispreferably added to the fluid suspension. The resulting flavored nutspreads are more fluid and softer than products made without using thefluid suspension. This invention does not provide for thecharacteristics of either liquid product homogeneity orself-emulsification and demonstrates a relatively high viscosity, whichmakes it irrelevant to this invention.

In U.S. Pat. No. 3,959,498 to Lyall there is described a one stepprocess for applying sugar and an edible fat or oil to cereal bases. Noseparate step of spraying the oil into the cereal substrate isnecessary. The invention also provides an emulsion cereal coating forachieving the above purpose, and a method of preparing said coating. Aquantity of edible fats or oils or other edible oil- or fat-derivedoleaginous material (5-32%) along with a quantity of emulsifier (0.5-5%)is added to an aqueous sugar solution (60-85% solids) to make up a syrupemulsion having a water content in the range of 9%-34% by weight. Theedible fat or oil and emulsifier are added to the aqueous syrup at atemperature ranging from 115° F., to 155° F. (46.1° C. to 68.3° C., andafter emulsification, the mixture is heated to about 180° F. (82.2° C.).As in the above example, this invention does not provide for thecharacteristics of either liquid product homogeneity orself-emulsification and demonstrates a relatively high viscosity, whichmakes it inapplicable to this invention. In addition it provides for anoil-in-water emulsion whereas the composition claimed herein is a liquidhomogeneous (solution or microemulsion) product.

SUMMARY OF THE INVENTION

The current invention involves the development of cold (0° C.), roomtemperature (about 20°-25° C.), and heat (e.g. about 50° C.) stablesystems comprising mixtures of a concentrated liquid) saccharide productwith an agricultural spray oil. These mixtures remain homogeneousliquids within the temperature range of about 0°-50° C. and areself-dispersing upon dilution in oil. The described homogeneous liquidscontain amounts of 0.5-50% by weight surfactant with oil:saccharideproduct ratios between 1:100 and 100:1 with the preferred compositionoccurring between 1:10 and 10:1; the more preferred composition between1:3 and 3:1; and the most preferred composition occurring between 1:2and 2:1.

The invention comprises the basic components of: a biologicallyefficacious oil, a liquid saccharide product (which are primarilyconcentrated, viscous water based syrups), and one or more surfactantsto deliver a stable, water dispersible, and homogeneous (solution ormicroemulsion) delivery system for agricultural adjuvants. One specificsurfactant composition or surfactant chemical type is not universallyrequired; using the understanding of interactions that was developed, abroad range of surfactant compositions were developed that were capableof delivering the described product.

Surfactant compositions that were used to develop such formulationsinclude but are not limited to alkylpolysaccharides, phosphate esters,sorbitan esters, mono- and diglycerides, polysorbates, and ethoxylatedalkylamines. Minor amounts of water may be used to effect thecompatibilization of oil:surfactant:saccharide systems; in no case wasmore than 25% water added to effect compatibilization. Surfactantsystems providing the desired homogeneity and compatibility weretypically used in the range of 10-40% with the more preferredcompositions containing 10-35%; and the most preferred compositionscontaining 10-25%.

Preferably the surfactant includes a non-ionic surfactant and is mostpreferably made entirely of one or more non-ionic surfactants. Ifdesired, other surfactants, such as at least one anionic surfactant, forinstance an anionic alkanolamine salt may be employed.

This invention relates to surfactant compositions and in particular tocompositions which contains a plurality of surfactants and at least oneoil, and which is readily emulsifiable into water.

The invention provides a concentrate composition which comprises:

-   a at least one oil component;-   b at least one non-surfactant saccharide,-   c at least one non-ionic surfactant.

The composition may also comprise at least one of the following:

-   d at least one surfactant hydrocarbyl saccharide; or-   e at least one anionic surfactant; or-   f at least one additional oil soluble non-ionic surfactant.

DETAILED DESCRIPTION OF THE INVENTION

The composition of the invention typically takes the form of anoil-based concentrate which is homogenous for at least 24 hours andwhich emulsifies readily on dilution into water. It will be used as aprecursor for dilution with water for agricultural spray mixturescontaining an agrochemical. Such spray mixtures will contain one or morepesticidally active ingredients and/or nutrients.

The concentrate composition may also comprise a water miscible liquid,which may be desirable if the viscosity of the composition wouldotherwise be inconveniently high. Such liquid may include or be water.The water content is preferably low enough for the composition to remainhomogenous for at least 24 hours after being made. The components andtheir proportions are preferably chosen such that where any componentsare readily available only as aqueous solutions, such as HFCS (highfructose corn syrup), the composition provided by mixing the compositioncomponents is stable, notwithstanding the water which is therebyintroduced. When the concentrate composition includes water, theconcentrate will usually be a solution of the water in the oil, thesurfactant combination acting to solublise the water, or as awater-in-oil colloidal emulsion or a microemulsion in which the water isdispersed as very fine droplets such that the composition is clear ortransparent.

The oil component typically has a boiling point of over about 200° C. atatmospheric pressure and a melting point not higher than about 60° C. Itmay comprise for example a mineral oil, an optionally hydrogenatedvegetable oil, such as an optionally hydrogenated cotton seed oil,linseed oil, mustard oil, neem oil, niger seed oil, oiticica oil, oliveoil, palm oil, palm kernel oil, peanut oil, perilla oil, poppy seed oil,rape seed oil, safflower oil, sesame oil, or soybean oil as well as anester (especially a C₁ to C₆ ester) of a C₈ to C₂₂ fatty acid(especially a C₁₂ to C₁₈ fatty acid) e.g. methyl, ethyl or propyllaurate, myristate, palmitate, palmitoleate, linoleate, linolenolate,stearate or oleate, or a mixture thereof, e.g. an ester in which thetotal number of carbon atoms in the molecule does not exceed 20, andpreferably an ester of a C₁₂ to C₁₈ fatty acid, e.g. methyl, ethyl orpropyl laurate, or a mixture thereof.

The oil component preferably also contains or is associated with atleast one oil soluble surfactant, especially one that can render the oilself-emulsifiable into water. Such a surfactant may include at least oneof relatively high HLB (hydrophilic lipophilic balance) in combinationwith one of low HLB, for example calcium stearate. Such an oil solutioncomponent may be in the form of a commercially available so-called “cropoil” or “oil adjuvant”. A typical oil component contains about 99 toabout 45, preferably about 90 to about 60, parts by weight of oil, andabout 1 to about 55, preferably about 10 to about 40, parts by weight ofoil soluble surfactant(s). When water is present in solublised form oras a colloidal emulsion or a microemulsion the oil soluble surfactantmay be partitioned between oil phase and aqueous phases (or be presentat the interface).

The liquid saccharide solution may be of a monosaccharide,oligosaccharide or a polysaccharide or mixture thereof; saccharides maybe linear, branched, or cyclic in nature. For such liquid saccharidesolutions, the solvent may be water, propylene glycol, or glycerol orany combination thereof. It is conventional to refer to liquidsaccharide solutions as syrups. Oligosaccharides present in solution arecommonly identified as maltodextrins while polysaccharides are commonlyidentified as dextrins. Among liquid saccharide solutions, compounds ofparticular use in this invention include compounds and mixtures ofcompounds described as HFCS, corn syrup, corn sweetener, invert sugar,invert sugar syrup, sugar, sugar syrup, and maltodextrins where theresulting liquid saccharide solution is homogeneous and stable for atleast 24 hours and contains about 75 parts by weight of water or less,preferably about 15 to about 50 parts by weight of water.

It is desirable that when the saccharide is an oligosaccharide of thegeneral formula:(C₆H₁₂O₆)_(n)—(H₂O)_(n−1)where n is greater than or equal to one and not more than fifty. Inparticular, the saccharide may be one in which the average value of n istypically at least 1 and not more than 5. A particularly useful materialof this type is one in which n has an average value of approximately 1and where the saccharide is a monosaccharide and the monosaccharide is aketo-sugar, most preferably fructose. Fructose is commercially availableas HFCS and the material designated for example as IsoClear 55 byCargill can be used satisfactorily.

The non-ionic surfactant(s) may be any which will give a compositionwhich is stable and homogeneous for at least 24 hours after being made.

Preferred non-ionic surfactants are of the formula:R¹.O.A_(n)R²  (I), orR³.N.(A_(n)R²)₂  (II)wherein

-   -   R¹ is a hydrocarbyl, hydrocarbonyl, or hydrocarbamidyl group,        which suitably contains from 6 to 24, preferably 8 to 22, and        especially 12 to 18 carbon atoms, a glycerol or polyglycerol        group, or a sorbitan or sorbitol group;    -   A is a polyalkylene oxide unit containing an average of n        alkylene oxide groups or mixed alkylene oxide groups, where the        alkylene groups each have 2 to 8, preferably 2 or 3, carbon        atoms;    -   n is between 0 and 40, preferably between 2 and 30, and most        preferably between 5 and 20;    -   R² is hydrogen or hydrocarbonyl residue having 8 to 22 carbon        atoms, or a polycarboxylic acid residue having 2 to 6 carbon        atoms such as malate, fumarate, maleate, succinate, or citrate,        or an oligomer thereof;    -   R³ is a hydrocarbyl or hydrocarbonyl group having 8 to 22 carbon        atoms, preferably 12 to 18.

The surfactant hydrocarbyl saccharide may be any which will give acomposition which is stable and homogeneous for at least 24 hours afterbeing made.

The surfactant hydrocarbyl saccharide may be a monoglycoside or apolyglycoside or mixture thereof. It is conventional to refer tohydrocarbyl saccharide surfactants as hydrocarbyl polysaccharides evenwhere the saccharide moiety only contains one saccharide unit. Typicallysuch surfactants are mixtures of compounds with monosaccharide andpolysaccharide (including disaccharide) units. Among glycosides,compounds of particular use in this invention include compounds andmixtures of compounds of the formula:ROG_(a)where

-   R is a hydrophobic moiety;-   G is a saccharide residue; and-   a has an average value of at least 1.

The group R may be an optionally substituted hydrocarbyl group. Inparticular R can be an alkyl, cycloalkyl, aryl, alkaryl, aralkyl oralkenyl group and is preferably an alkyl group. The group R suitablycontains from 4 to 30 carbon atoms, preferably up to 24 carbon atoms,more preferably from 6 to 18 carbon atoms and especially from 8 to 14carbon atoms. Thus, R can be a mixture of alkyl or alkoxy groups whichcontain, on average, for example 8 to 14 carbon atoms.

The saccharide residue G may be derived from one or more of fructose,glucose, mannose, galactose, telose, gulose, allose, altrose, idose,arabinose, xylose, lyxose and ribose or from mixtures thereof. The groupG is conveniently derived from glucose units and the glycoside is then aglucoside. If derived from sucrose the groups will comprise fructose andglucose residues.

The value of a is the degree of polymerisation. It typically has anaverage value of at least 1.1, preferably at least 1.2 and especially atleast 1.3. The value of a is typically not greater than 8, andpreferably not greater than 4, for example not greater than 2. When theglycoside is an alkyl glucoside, the value of a is conveniently between1 and 2.

Desirable results are obtained when the glycoside is an alkylpolyglucoside of the general formula:C_(n)H_((2n+1)).O.(C₆H₁₀O₅)_(b).Hwhere

-   n is from 8 to 14, and-   b is greater than one and not more than two.

In particular, the glucoside may be one in which the average value of nis from 9 to 13 and especially about 10. The value of b is typically atleast 1.3 and not more than 1.9. A particularly useful material of thistype is one in which n is from 8 to 11 and has an average value of 10and b is about 1.35. Surfactant hydrocarbyl saccharides are commerciallyavailable and the materials designated for example as Atplus 452 andAtplus 438 by Uniqema or as sold under the trade name Triton BG 10 byDow Chemicals can be used satisfactorily.

The anionic surfactant(s) may be any which will give a composition whichis stable and homogeneous for at least 24 hours after making up.

The anionic surfactant(s) may be any which will give a composition whichis stable and homogeneous for at least 24 hours after making up. It ischaracterized as at least one anionic surfactant compound of the generalformula:R¹.O.A_(n)—X  (I), orR¹—X  (II)where

-   R¹ is a hydrocarbyl group having 6 to 24 carbon atoms, preferably 8    to 22 carbon atoms, and most preferably 12 to 18 carbon atoms;-   A is a polyalkylene oxide unit containing an average of n alkylene    oxide groups or mixed alkylene oxide groups, where the alkylene    groups each have 2 to 8, preferably 2 or 3, carbon atoms;-   n is between 0 and 60, preferably between 2 and 30, and most    preferably between 3 and 15;-   X is a group including at least one acidic H atom or salt thereof,    desirably an amine salt.

In the foregoing formula X is a group including at least one acidic atomor a salt thereof, by which is meant that the group X can be ionized toform an anionic group in an aqueous medium. The group thus provides ananionic function, thereby making the surfactant anionic. This functioncan be a partially or fully oxidized phosphorus, sulfur, or carbon acidgroup.

The other non-ionic surfactant(s) may be any which will give acomposition which is stable and homogeneous for at least 24 hours afterbeing made.

Desirable results are particularly obtained when the non-ionicsurfactant is of the general formula (I) or (II):R¹.O.A_(n)R²  (I), orR³.N.(A_(n)R²)₂  (II)wherein

-   -   R¹ is a hydrocarbyl, hydrocarbonyl, or hydrocarbamidyl group,        which suitably contains from 6 to 24, preferably 8 to 22, and        especially 12 to 18 carbon atoms, a glycerol or polyglycerol        group, or a sorbitan or sorbitol group;    -   A is a polyalkylene oxide unit containing an average of n        alkylene oxide groups or mixed alkylene oxide groups, where the        alkylene groups each have 2 to 8, preferably 2 or 3, carbon        atoms;    -   n is between 0 and 40, preferably between 2 and 30, and most        preferably between 5 and 20;    -   R² is hydrogen or a hydrocarbonyl group having 8 to 22 carbon        atoms, or a polycarboxylic acid residue having 2 to 6 carbon        atoms such as malate, fumarate, maleate, succinate, or citrate,        or an oligomer thereof;    -   R³ is a hydrocarbyl or hydrocarbonyl group having 8 to 22 carbon        atoms, preferably 12 to 18.

The relative proportions of the oil component (a), the liquid saccharidesolution (b), and the non-ionic surfactant (c) are suitably (by weight):

-   a 10 to 90, especially 25 to 75, preferably 30 to 60,-   b 10 to 90, especially 15 to 45, preferably 20 to 40, and-   c 5 to 80, especially 5 to 60, preferably 10 to 45.    and optionally at least one surfactant hydrocarbyl saccharide (d);    or anionic surfactant (e); or non-ionic surfactant (f) the    proportions are as follows:-   d 1 to 20, especially 2 to 15, preferably 3 to 10, or-   e 1 to 20, especially 2 to 15, preferably 3 to 10, or-   f 1 to 20, especially 2 to 15, preferably 3 to 10.

Any chemical agent specific to the intended use of the composition willbe an agrochemical. The agrochemical is typically one or more nutrients,growth regulators, herbicides, and/or pesticides, for exampleinsecticides, fungicides or acaricides.

The invention includes a process for making the composition of theinvention which comprises mixing the components together.

The invention further includes a diluted formulation which comprises acomposition comprising components (a), (b) and (c) according to theinvention with from about 10 to about 10,000 times the weight of thecomposition of water. The concentrate compositions of the inventionemulsify readily on dilution in water to form the formulation. Atrelatively low levels of dilution, the product will be an oil-in-wateremulsion having a relatively high concentration of oil. Thisintermediate emulsion subsequently can be further diluted by water or anaqueous solution or suspension of other components desired in the finalformulation.

The diluted formulations can be made up in various ways. Thus, aformulation comprising components other than (a), (b), (c) andoptionally one or more of components (d), (e), or (f) and water, can bemade up by simply mixing the composition of components (a), (b), (c) andoptionally one or more of components (d), (e), or (f) with water.

In a further aspect, the invention provides a method of applying aformulation of the invention to a substrate. Embodiments of this methodinclude a method of treating vegetation by applying to plants and/orsoil such a formulation according to the invention which formulationcomprises a specific chemical agent which is an agrochemical.

In this embodiment the agrochemical may be one or more growthregulators, herbicides, and/or pesticides, for example insecticides,fungicides or acaricides. This embodiment of the invention of the methodof applying the formulation accordingly includes: a method of killing orinhibiting vegetation by applying the formulation which comprises aspecific chemical agent which is one or more growth regulators and/orherbicides, and a method of killing or inhibiting plant pests byapplying the formulation which comprises a specific chemical agent whichis one or more pesticides, for example insecticides, fungicides oracaricides.

In this embodiment, the effect of the agrochemical, whether one or moregrowth regulators, herbicides, and/or pesticides, for exampleinsecticides, fungicides or acaricides, may be potentiated by the oilcomponent and/or the saccharide and/or the surfactant compositionpresent in the composition.

Examples of the agrochemical which is typically one or more growthregulators, herbicides, and/or pesticides, for example insecticides,fungicides or acaricides, particularly growth regulators, herbicides,etc. include phosphonomethyl-n-carboxymethyl (PMCM) compounds andrelated compounds of the formula:R⁷.C(O).CH₂N(Z).CH₂P(O).(R⁷)₂where

-   each R⁷ is independently halogen, —NHOH, —N(R⁸)₂, —OR⁹, —SR⁹ or —OM,    where-   R⁸ is independently a hydrogen, or alkyl or hydroxyalkyl, preferably    containing less than about 5 carbon atoms, alkenyl, preferably    containing less than about 5 carbon atoms, or phenyl; each R⁹ is    independently hydrogen, alkyl, hydroxyalkyl or chloroalkyl,    preferably containing less than about 5 carbon atoms, alkoxy,    preferably containing less than about 5 carbon atoms, alkylene    amine, preferably containing less than about 12 carbon atoms, phenyl    or benzyl; M is hydrogen or an agriculturally acceptable salt    forming moieties such as alkali metal, alkaline earth metal,    stannic, ammonium, organic ammonium, alkyl sulfonium, alkyl    sulfoxonium, alkyl phosphonium moieties or combinations thereof, and    Z is hydrogen, an organic moiety or an inorganic moiety.

Representative patents disclosing at least some of such compoundsinclude U.S. Pat. Nos. 3,799,758, 4,397,676, 4,140,513, 4,315,765,3,868,407, 4,405,531, 4,481,026, 4,414,158, 4,120,689, 4,472,189,4,341,549 and 3,948,975. Patents disclosing PMCM compounds wherein Z isother than hydrogen include U.S. Pat. Nos. 3,888,915, 3,933,946,4,062,699, 4,119,430, 4,322,239 and 4,084,954.

In preferred PMCM compounds,

-   Z is hydrogen or an organic substituent;-   R⁹ is independently selected from hydrogen, alkyl, hydroxyalkyl or    chloroalkyl, preferably containing less than about 5 carbon atoms,    alkoxy, preferably containing less than about 5 carbon atoms,    alkylene amine, preferably containing less than about 12 carbon    atoms, phenyl or benzyl moieties; and-   M is selected from hydrogen and agriculturally acceptable salt    forming moieties, alkali metal, phosphonium moieties or combinations    thereof.

Representative patents disclosing at least some of such compoundsinclude U.S. Pat. Nos. 3,799,758, 4,397,676, 4,140,513, 4,315,765,3,868,407, 4,405,531, 4,481,026, 4,414,158, 4,120,689, 4,472,189,4,341,549 and 3,948,975. Patents disclosing PMCM compounds wherein Z isother than hydrogen include U.S. Pat. Nos. 3,888,915, 3,933,946,4,062,699, 4,119,430, 4,322,239 and 4,084,954.

In preferred PMCM compounds, Z is hydrogen or an organic substituentsuch as methylene carboxylic; methylene phosphonic; and methylene cyano.Other organic substituents include carboxyl, such as formyl, acetyl,benzoyl, perfluoroacyl and thiocarbonyl; ethylene, such as cyano,carbamoyl or carboxy substituted ethyl; and benzene sulphonylsubstituents. Patents disclosing compounds where the nitrogen has threeorganic substituents include U.S. Pat. Nos. 3,455,675, 3,556,762,3,853,530, 3,970,695, 3,988,142, 3,991,095, 3,996,040, 4,047,927,4,180,394, 4,203,756, 4,261,727 and 4,312,662. A preferred tertiarynitrogen substituted PMCM compound is N,N-bis(phosphonomethyl)glycine.

Those PMCM compounds where Z is hydrogen are most preferred when thephytoactivity desired is herbicidal activity.

The above listed patents are incorporated herein by reference.

Illustrative examples of agriculturally acceptable salt forming moietiesrepresented by M, as in OM, are the alkali metals having atomic weightsof from 22 to 133, inclusive, such as sodium, potassium, or rubidium;the alkaline earth metals having atomic weights of from 24 through 88inclusive, such as magnesium or calcium; ammonium and aliphaticammonium, wherein the aliphatic is primary, secondary, tertiary orquaternary and preferably wherein the total number of carbon atoms doesnot exceed more than about twelve; phenylammonium; trialkylsulphonium,preferably wherein the total number of carbons in the three alkylsubstituents does not exceed more than about six, such astrimethylsulphonium, ethyl dimethylsulphonium, propyl dimethylsulphoniumand the like; trialkylsulphoxonium, preferably wherein the total numberof carbon atoms in the three alkyl substituent does not exceed more thanabout six, such as trimethylsulphoxonium, ethyl dimethylsulphoxonium,propyl dimethylsulfoxonium and the like; tetraalkylphosphonium, such astetramethylphosphonium, ethyl trimethylphosphonium,propyltrimethylphosphonium and similar groups.

In desirable compositions according to this invention, M isindependently selected from the above described agriculturallyacceptable salt forming moieties and hydrogen. In more desirablecompositions, M is an alkali metal, ammonium, monoalkyl ammonium ortrialkylsulphonium moiety. In especially desirable compositions only oneM is an alkali metal, ammonium, monoalkyl ammonium, ortrialkylsulphonium moiety, while the two M's are hydrogen.

Particularly desirable compositions include isopropylamineN-phosphonomethylglycine, trimethylsulphonium N-phosphonomethylglycineand sodium sesqui-N-phosphonomethylglycine. Combinations of two or morePMCM compounds can be employed in the composition formulation andmethods of the present invention.

The following examples are illustrative of the present invention. Allamounts are by weight unless otherwise indicated.

EXAMPLE 1

The following concentrate is prepared:

Component code Component Name Wt. Amount a Mineral oil 44.12 b HighFructose Corn Syrup solution 29.41 c Ethoxylated tallowamine 26.47

The foregoing concentrate self-emulsifies upon 5% dilution in water.When 0.5% (v/v) parts of the agrochemical glyphosate is incorporatedinto the concentrate prior to dilution in water the diluted compositionis effective as a herbicide.

EXAMPLE 2

The following concentrate is prepared:

Component code Component Name Wt. Amount a Mineral oil 46.15 b HighFructose Corn Syrup 15.38 c Ethoxylated tallowamine 30.77 d C₉–C₁₁alkylpolysaccharide 7.69

The foregoing concentrate self-emulsifies upon 5% dilution in water.When 0.5% (v/v) parts of the agrochemical glyphosate is incorporatedinto the concentrate prior to dilution in water the diluted compositionis effective as a herbicide.

EXAMPLE 3

The following concentrate is prepared:

Component code Component Name Wt. Amount a Mineral oil 45.45 b HighFructose Corn Syrup solution 18.16 c Ethoxylated tallowamine 30.30 eDodecylbenzenesulfonate, 6.06 isopropylamine salt

The foregoing concentrate self-emulsifies upon 5% dilution in water.When 0.5% (v/v) parts of the agrochemical glyphosate is incorporatedinto the concentrate prior to dilution in water the diluted compositionis effective as a herbicide.

EXAMPLE 4

The following concentrate is prepared:

Component code Component Name Wt. Amount a Mineral oil 42.55 b HighFructose Corn Syrup solution 25.55 c Ethoxylated tallowamine 28.37 fSorbitan monooleate 3.55

The foregoing concentrate self-emulsifies upon 5% dilution in water.When 0.5% (v/v) parts of the agrochemical glyphosate is incorporatedinto the concentrate prior to dilution in water the diluted compositionis effective as a herbicide.

EXAMPLE 5

The following concentrate is prepared:

Component code Component Name Wt. Amount a Mineral oil 44.12 b HighFructose Corn Syrup solution 14.71 c Ethoxylated tallowamine 29.41 dC₉–C₁₁ alkylpolysaccharide 8.82 f Mono- and di-glycerides 2.94

The foregoing concentrate self-emulsifies upon 5% dilution in water.When 0.5% (v/v) parts of the agrochemical glyphosate is incorporatedinto the concentrate prior to dilution in water the diluted compositionis effective as a herbicide.

EXAMPLE 6

The following concentrate is prepared:

Component code Component Name Wt. Amount a Mineral oil 43.17 b HighFructose Corn Syrup solution 18.71 c Ethoxylated tallowamine 28.78 eDodecylbenzenesulfonate, 7.19 isopropylamine salt f Sorbitan monooleate2.16

The foregoing concentrate self-emulsifies upon 5% dilution in water.When 0.5% (v/v) parts of the agrochemical glyphosate is incorporatedinto the concentrate prior to dilution in water the diluted compositionis effective as a herbicide.

EXAMPLE 7

The following concentrate is prepared:

Component code Component Name Wt. Amount a Mineral oil 33.78 b HighFructose Corn Syrup solution 14.93 c Ethoxylated tallowamine 29.85 dC₉–C₁₁ alkylpolysaccharide 7.46 e Dodecylbenzenesulfonate, 2.99isopropylamine salt

The foregoing concentrate self-emulsifies upon 5% dilution in water.When 0.5% (v/v) parts of the agrochemical glyphosate is incorporatedinto the concentrate prior to dilution in water the diluted compositionis effective as a herbicide.

EXAMPLE 8

The following concentrate is prepared:

Component code Component Name Wt. Amount a Mineral oil 37.97 b HighFructose Corn Syrup solution 25.32 c Ethoxylated tallowamine 25.32 dC₉–C₁₁ alkylpolysaccharide 6.33 e Dodecylbenzenesulfonate, 2.53isopropylamine salt f Sorbitan monooleate 2.53

The foregoing concentrate self-emulsifies upon 5% dilution in water.When 0.5% (v/v) parts of the agrochemical glyphosate is incorporatedinto the concentrate prior to dilution in water the diluted compositionis effective as a herbicide.

One skilled in the art will appreciate that the present invention can bepracticed by other than the described embodiments that are presented forpurposes of illustration and not of limitation

The invention claimed is:
 1. A homogeneous and self-emulsifyingoil-based agrochemical concentrate composition, comprising: a) from 30to 60 parts by weight of at least one oil component; b) from 15 to 40parts by weight of high fructose corn syrup; c) from 5 to 45 parts byweight of at least one non-ionic surfactant, of the formula:R¹—O—A_(n)R²  (I), orR³—N—(A_(n)R²)₂  (II); and d) at least one of the following additionalcomponents: i) from 1 to 20 parts by weight of at least one surfactanthydrocarbyl saccharide; ii) from 1 to 20 parts by weight of at least oneanionic surfactant; or iii) from 1 to 20 parts by weight of at least onefurther non-ionic surfactant; wherein: R¹ represents a hydrocarbyl,hydrocarbonyl, or hydrocarbamidyl group having from 6 to 24 carbonatoms, a glycerol or polyglycerol group, or a sorbitan or sorbitolgroup; A represents a polyalkylene oxide unit containing an average of nalkylene oxide groups or mixed alkylene oxide groups, wherein thealkylene groups each have 2 to 8 carbon atoms; n represents a valuebetween 0 and 40; R² represents a hydrogen or hydrocarbonyl residuehaving 8 to 22 carbon atoms, or a polycarboxylic acid residue of malate,fumarate, maleate, succinate, or citrate, or an oligomer thereof; and R³represents a hydrocarbyl or hydrocarbonyl group having 8 to 22 carbonatoms; and wherein the total surfactant comprises from 10% to 50% byweight of the concentrate.
 2. The agrochemical concentrate compositionof claim 1, wherein each of the at least one of the additionalcomponents of d) are present.
 3. The agrochemical concentratecomposition of claim 1, wherein the at least one of the additionalcomponents of d) is present in an amount of from 2 to 15 parts byweight.
 4. The agrochemical concentrate composition of claim 2, whereinthe at least one of the additional components of d) is present in anamount of from 2 to 15 parts by weight.
 5. The agrochemical concentratecomposition of claim 1, wherein the oil component has a boiling point ofover 200 ° C.
 6. The agrochemical concentrate composition of claim 1,wherein the oil component comprises a mineral oil, a vegetable oil, anester of a C₈ to C₂₂ fatty acid, or a mixture of more than one of these.7. The agrochemical concentrate composition of claim 1, wherein thenon-ionic surfactant component is one or more of the following: analkoxylated fatty acid, a polyalkylene glycol ester, an alkoxylatedglyceride, an alkoxylated sorbitan and/or a sorbitol ester, analkylphenol alkoxylate, an alcohol alkoxylate, an alkylamine alkoxylate,an alkanolamide and/or an alkoxylated alkanolamide.
 8. The agrochemicalconcentrate composition of claim 1, wherein: i) the at least onesurfactant hydrocarbyl saccharide component is of the formula:ROGa wherein: R represents a hydrophobic moiety; G represents asaccharide residue; and a represents an average value of at least 1; ii)the at least one anionic surfactant component is of the formula:R¹—O—A_(n)—Xtm (I), orR¹—Xtm (II) wherein: R¹ represents a hydrocarbyl group having 6 to 24carbon atoms; A represents a polyalkylene oxide unit containing anaverage of n alkylene oxide groups or mixed alkylene oxide groups, wherethe alkylene groups each have 2 to 8 carbon atoms; n represents a valuebetween 0 and 60; and X represents a group including at least one acidicH atom or salt thereof; and iii) the at least one further non-ionicsurfactant component is of the formula:R¹—O—A_(n)R²  (I), orR³—N—(A_(n)R²)₂  (II) wherein: R¹ represents a hydrocarbyl,hydrocarbonyl, or hydrocarbamidyl group having from 6 to 24 carbonatoms, a glycerol or polyglycerol group, or a sorbitan or sorbitolgroup; A represents a polyalkylene oxide unit containing an average of nalkylene oxide groups or mixed alkylene oxide groups, where the alkylenegroups each have 2 to 8 carbon atoms; n represents a value between 0 and40; R² represents hydrogen or a hydrocarbonyl group having 8 to 22carbon atoms, or a polycarboxylic acid residue of malate, fumarate,maleate, succinate, or citrate, or an oligomer thereof; and R³represents a hydrocarbyl or hydrocarbonyl group having 8 to 22 carbonatoms.
 9. The agrochemical concentrate composition of claim 8, wherein:the at least one alkyl polysaccharide component is an alkylpolyglucoside of the general formula:C_(n)H(_(2n+1))—O—(C₆H₁₀O₅)_(b)H where n is from 8 to 14 and b isgreater than or equal to one and less than three.
 10. The agrochemicalconcentrate composition of claim 9, wherein the at least one anionicsurfactant component is one or more of the following: an alkylcarboxylate and/or an alkyl ether carboxylate, an alkyl sulfate and/oran alkyl ether sulfate or alkylphenyl ether sulfate, an alkyl phosphateor an alkylphenyl phosphate and/or an alkyl ether phosphate oralkylphenyl ether phosphate, an alkyl sulfosuccinate or an alkylphenylsulfosuccinate and/or an alkyl ether sulfosuccinate or an alkylphenylether sulfosuccinate, an alkyl sulfonate or an alkylphenyl sulfonate,and/or an alkyl phosphonate or an alkylphenyl phosphonate.
 11. Theagrochemical concentrate composition of claim 9, wherein at least onefurther non-ionic surfactant component is one or more of the following:glycerol or a polyglycerol ester, sorbitol or a sorbitan ester, anethylene glycol ester or a propylene glycol ester, a polyethylene glycolester and/or a fatty alcohol.
 12. A homogeneous and self-emulsifyingoil-based agrochemical concentrate composition, comprising: a) from 30to 60 parts by weight of at least one oil component; b) from 15 to 40parts by weight of high fructose corn syrup; c) from 5 to 45 parts byweight of at least one C₈ to C₂₂ hydrocarbyl amine alkoxylatesurfactant, wherein said surfactant comprises from 10% to 50% by weightof the concentrate; and d) at least one of the following additionalcomponents: i) from 1 to 20 parts by weight of at least one surfactanthydrocarbyl saccharide; ii) from 1 to 20 parts by weight of at least oneanionic surfactant; or iii) from 1 to 20 parts by weight of at least onefurther non-ionic surfactant.
 13. The agrochemical concentratecomposition of claim 12, wherein each of the at least one of theadditional components of d) are present.
 14. The agrochemicalconcentrate composition of claim 12, wherein the at least one of theadditional components of d) is present in an amount of from 2 to 15parts by weight.
 15. The agrochemical concentrate composition of claim12, wherein the oil component has a boiling point of over 200° C. 16.The agrochemical concentrate composition of claim 12, wherein the oilcomponent comprises a mineral oil, a vegetable oil, an ester of a C₈ toC₂₂ fatty acid, or a mixture of more than one of these.
 17. Theagrochemical concentrate composition of claim 12, wherein the non-ionicsurfactant component is an alkylamine ethoxylate.
 18. The agrochemicalconcentrate composition of claim 12, wherein the non-ionic surfactantcomponent further includes one or more of the following: an alkoxylatedfatty acid, a polyalkylene glycol ester, an alkoxylated glyceride, analkoxylated sorbitan and/or a sorbitol ester, an alkylphenol alkoxylate,an alcohol alkoxylate, an alkanolamide and/or an alkoxylatedalkanolamide.
 19. The agrochemical concentrate composition of claim 12,wherein: i) the at least one surfactant hydrocarbyl saccharide componentis of the formula:ROGa wherein: R represents a hydrophobic moiety; G represents asaccharide residue; and a represents an average value of at least 1, ii)the at least one anionic surfactant component is of the formula:R¹—O—A_(n)—X  (I), orR¹—X  (II) wherein: R¹ represents a hydrocarbyl group having 6 to 24carbon atoms; A represents a polyalkylene oxide unit containing anaverage of n alkylene oxide groups or mixed alkylene oxide groups,wherein the alkylene groups each have 2 to 8 carbon atoms; n representsa value between 0 and 60; and X represents a group including at leastone acidic H atom or salt thereof; and iii) the at least one additionalnonionic surfactant component is of the formula:R¹—O—A_(n)R²   (I), orR³—N—(A_(n)R²)₂   (II) wherein: R¹ represents a hydrocarbyl,hydrocarbonyl, or hydrocarbamidyl group having from 6 to 24 carbonatoms, a glycerol or polyglycerol group, or a sorbitan or sorbitolgroup; A represents a polyalkylene oxide unit containing an average of nalkylene oxide groups or mixed alkylene oxide groups, where the alkylenegroups each have 2 to 8 carbon atoms; n represents a value between 0 and40; R² represents hydrogen or a hydrocarbonyl group having 8 to 22carbon atoms, or a polycarboxylic acid residue of malate, fumarate,maleate, succinate, or citrate, or an oligomer thereof; and R³represents a hydrocarbyl or hydrocarbonyl group having 8 to 22 carbonatoms.
 20. The agrochemical concentrate composition of claim 19,wherein: the at least one surfactant hydrocarbyl saccharide component isan alkyl polyglucoside of the general formula:C_(n)H(_(2n+1))—O—(C₆H₁₀O₅)_(b)H where n is from 8 to 14 and b isgreater than or equal to one and less than three.
 21. The agrochemicalconcentrate composition of claim 19, wherein the at least one anionicsurfactant component is one or more of the following: an alkylcarboxylate and/or an alkyl ether carboxylate, an alkyl sulfate and/oran alkyl ether sulfate or alkylphenyl ether sulfate, an alkyl phosphateor an alkylphenyl phosphate and/or an alkyl ether phosphate or analkylphenyl ether phosphate, an alkyl sulfosuccinate or an alkylphenylsulfosuccinate and/or an alkyl ether sulfosuccinate or an alkylphenylether sulfosuccinate, an alkyl sulfonate or an alkylphenyl sulfonate,and/or an alkyl phosphonate or an alkylphenyl phosphonate.
 22. Theagrochemical concentrate composition of claim 19, wherein the at leastone further non-ionic surfactant component is one or more of thefollowing: a glycerol or a polyglycerol ester, a sorbitol or a sorbitanester, an ethylene glycol ester or a propylene glycol ester, apolyethylene glycol ester and/or a fatty alcohol.
 23. A homogeneous andself-emulsifying oil-based agrochemical concentrate composition whichcomprises: a) 30-60 parts by weight of mineral oil; b) 15-40 parts byweight of high fructose corn syrup; and c) 10-45 parts by weight ofethoxylated tallowamine, wherein the ethoxylated tallowamine comprises10-50% by weight of the concentrate; and further comprises at least oneof the following additional components: d) 2-10 parts by weight of aC₉-C₁₁ alkyl polysaccharide; e) 2-10 parts by weight ofdodecylbenzenesulfonate, isopropylamine salt; and f) 2-10 parts byweight of sorbitan monooleate.
 24. The agrochemical concentratecomposition of claim 23, wherein each of the at least one of theadditional components of d), e), and f), are present.